Method of producing colored colloid layers for photographic purposes and material therefor



Nov. 22,1938. g A AR 2,137,336

METHOD OF PRODUCING COLOREO COLLOID LAYERS FOR PHOTOGRAPHI C PURPOSES AND MATERIAL THEREFOR Filed June 20, 1936 L1 ht Lightseh ifa g afifj hfi LagerContammg,

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S upporf I Light Sensitive Fastl Dyed Llghf Lager Contain ng, sens Ltl Ve Lage Preclp g Agent ATTORNEY Patented Nov. 22,1938 I 1 UNITED STATES METHOD or raonucmo ooLonEn col.- Y Loin amas ron rno'roensrmo run.- rosns AND MATERIAL 'rnsanroa Bela. Gaspar, Brussels, Belgium Application June 20, 1936, .Serial No. 88,427

In Germany June 21, 1935 13 Claims.

For many purposes in connection with photo graphic and color photographic processes it is necessary to produce colored gelatine layers, the color of which does not bleed or, in the case oi l a plurality of layers, diffuse from one colored layer into an adjacent layer which may beeither colorless'or-may be difi'erentlycolored. It has been proposed to mordant the dyestufis used for dyeing the gelatine by treating the layer after dyeing with metal salts. It has also been proposed to precipitate the dyestuil. within the emulsion prior, to pouring. Furthermore for the same purpose it is known to cause mutualprecipitation of dyestuifs of contrary reaction or to eifect double l5 decomposition of dyestuffs and precipitating agents, a diflicultly soluble salt of the dyestuif being formed by this double decomposition. Diffusion of the dyestufis present in adjacent layers of a multilayer material has been prevented by the formation in the boundary zone of such layers of an extremely dispersed dyestufl? precipitate produced by mutual precipitation of the dyestufls contained in each of the layers or of one dyestuil' contained in one of the layers and a colorless'precipitating agent present within the other layer. Applicant has discovered, contrary to what might be expected, that such dyestufi precipitates 'in the boundary zone are no'obstacle to'difiusion of dyestuffs from aqueous solution through the boundary zone into the deeper strata of the gelatine. Even with thick layers of gelatine, containing a precipitating agentand in which a very finely dispersed dyestufi precipitate is formed by treating with aqueous dyestuii' solution, there is no difilculty for complete dyeing of the gelatine. For example, it has been found, that a gelatine layer containing diphenyl-guanidine acetate allows penetration of a solution of 1% strength of Diamine Pure Blue (Schultz Farbstofitabelien 5th Ed. No. 426). An insoluble'diphenyl-guanidine salt is formed at the surface of the layer, but nevertheless the penetration of the dissolved dyestufi is not inhibited and further quantities of the .dyestufl are precipitated within the deeper strata of the gelatine. When interrupting the treatment with the solution of the blue dyestufl' and continuing for example with a solution of Xylene Light Yellow 2G (Schultz, l. c. No. 22) the deepest stratum of the gelatine will be dyed yellow. These phenomena may be used for dyeing and especially selectively dyeing of gelatine layers for photographic purposes which layers may contain lightsensitive silver salts or already exposed and developed silver images.

55, According to the invention the gelatine layers to be colored by a water-insolubie'precipitate of water-soluble dyestuffs are produced by adding the precipitating agent to the gelatine either before pouring the same or to the layer coated on a support, and'applying thereafter an aqueous solu- 5 tion of the dyestufl' to the coating. The addition of the precipitating agent-to the gelatine or emulsion prior to coating is preferable if it is desired to have a distinct amount 01 dyestuil precipitated within the layer, as the quantity of precipitating 1o agent determines to a great extent the quantity of dyestuii' fixed. especially if dyestuffs are used which by themselves do not dye the gelatine. Sometimes it may be desirable to add the precipitating agent only after pouring the layer and 15 then a solution of the precipitating agent may be applied prior'to the treatment with the dyestuif solution. r r

The addition of the precipitating agent to the gelatine or gelatine-layer and the subsequent dye- 2,0

ing with a dyestufl, which is precipitated by the agent present within the layer, may be used for selectively dyeing a plurality of layers poured one on top of the'other or for dyeing diflerent strata of a single layer. Even a layer not situated at the 26 surface of a multilayer-material-can be selectively dyed and the coloration so obtained does not diiffuse or bleed. Therefore the exposure of the partlayers of. a multi-layer light-sensitive material may occur while these layers are colorless and the 30 dyestufls necessary for the color reproduction may be applied afterexposure. Thereafter the dyestuffs uniformly applied to and precipitated within the layers or part-layers. may be locally destroyed at the exposed or unexposed parts of the 35 layer by the use of the well-known dyestuil' destroying processes. A plurality of superimposed layers may be dyed a different color, either by using in each layer a precipitating agent which only precipitates one of the two diflerent dye- 40 I stuifs, or by using two dyestufi' solutions in succession, of which solutions the second forms a dyestufl deposit in the deepest part-layer, in which the precipitating agent is still present, whereas the superimposed layer is unaffected, the precipi- 45 tating agent having beenalready'consumed by the first treatment with the dyestufl solution. When using a plurality of precipitating agents the agent for the deeper layer is applied to the gelatine or emulsion prior to coating. The pre- 5 cipitating' agent for the top-layer may be applied after dyeing the deeper layer and the second dyestuii solution is applied thereafter.

Example 1.-A solution of 5 g. gelatine in 80 com. water is mixed with a solution oi 1 g. betaquinolin hydrochloride and Metanil naphthoquinolinium-N-ethyl sulphate and poured on to a support. The layer is treated with an aqueous solution of 1% strength of Dlamine Pure BlueFF (Schultz, l. c. No. 424).

Example 2.-A layer as described in Example 1 is treated with a solution of strength of Diamine Fast Red F (Schultz l. c. No. 343) The layer is used as an antihalation layer, a light sensitive emulsion being applied after drying of the colored layer.

Example 3.A"silver-bromide gelatine emulsio is colored yellow by adding 2-phenyl-4-amino- Yellow (Schultz l. c. No. 134). The emulsion is a sensitized emulsion, containing pinacyanol. After coating a colorless silver bromide gelatine emulsion containing 3 g. diphenyl-guanidin-acetate per sq. m. is coated on top of the yellow layer. After exposure'and development and fixing the film is treated by a solution of 1% strength of Diamine Pure Blue FF.

. Example 4.On to a yellow layer as described in Example 3 a colorless silver halide emulsion without the addition of a precipitating agent is poured. After exposure development and fixing a solution of strength of betanaphthoquinolinium-N-ethyl sulphate is applied and the mm is treated for about 10 minutes. Thereafter a dyestuif solution, as described in Example 3, is used for dyeing during about 4 minutes. The

vfilm then shows a blank silver image in the yellow dyed layer and a silver image in the blue dyed layer. The silver images are treated with a solution of 5% thiocarbamide and citric acid which, in a known manner, destroys the dyesturl's at the points where silver is present.

The film described may be used as a front film of a bipack, the rear film being a. colorless or colored film sensitive for grr en. In this case the blue sensitive layer of the double coated film faces the objective in the camera during exposure.

Example 5.-A silver bromide gelatine emulsion is dyed with chlorantinlichtgelb, (a dyestufl furnished by the Gesellschaft fiir Chemlsche Industrie, Basel, Switzerland) the dyestufl. being precipitated by barium nitrate. The emulsion is poured on a support and on top of the yellow layer a colorless silver bromide gelatine emulsion containing 3 g. of cinchonine hydrochloride per sq. m. is poured. The yellow layer may contain a sensitizer for red light or for green light, the top layer being an ordinary bluesensitive emulsion layer. After exposure the surface layer is treated with a solution of strength of Diamine Pure Blue or with a solution of Diamine Fast Pink BBF. The film is then developed and fixed and the dyestufi destroyed by a thiocarbamide solution at the points where silver is present.

Example 6.A silver halide emulsion containing 0.3% of the sodium salt of salicylic acid is poured on to a support of Celluloid. On top of this colorless layer a layer is poured containing Diamine Pure Blue precipitated by triphenylguanldine acetate. The composite film is treated after exposure by. an aqueous solution of strength of auramine (Schultz l. c. 49 and washed in water until the upper layer has become pure blue. The film as a whole appears green.

Instead of the dyestuffs used in the preceding examples other dyestuffs may be used which are precipitated by the precipitating agent contained in the layer. For dyeing of the deeper layers dyestuffs are used which do not dye the upper layer already colored but can be removed from the upper layer by washing. For dyeingof the surface layer acid and substantive dyestuffs are preferred and therefore precipitating agents are used which form insoluble salts by double decomposition with acid or substantive dyestuffs. There may be used, for example, the salts of organic bases, such as naphthoquinoline, triphenyl-guanidine, quinine, cinchonine, aminoquinoline. The salts formed by these bases with organic acids or the quaternary salts derived from the amines may be used. Other precipitating agents which may be used are inorganic bases or salts, such as barium carbonate or magnesium carbonate. For the precipitation of basic dyestuffs, such as chrysoidine (Schultz l. c. 33) or Janus-red-B (Schultz l. c. 240) antimony salts or zinc-ferrocyanide may be used or acids, such as tannic acids which form insoluble salts with basic dyestuffs. The amount of the precipitating agent and the sequence may be chosen according to the properties of dyestuff and precipitating agent or the desired result.

Instead of the dyestufi. solutions described 1 there may be used solutions which do not contain a dyestufi itself, but which form a dyestuif by interaction with dyestuff-forming substances present in the material. For example, a layer may beused which contains a leuco-derivatlve of a vat-dyestuff and a precipitating agent for the vat-dyestuifs. When such a layer is treated with an oxidizing agent the dyestufi is precipitated in situ by the precipitating agent and there is no possibility for bleeding or diffusion of the dyestuff.

Example 7.-A silver bromide gelatine emulsion which contains 20 g. silver bromide in one liter of emulsion and sensitized to red light with pinacyanol is coated onto a support of Celluloid.

To this emulsion is added before the coating operation either:

A. 5 g. of the beta-naphthothiazolium salt of diazo light yellow G dissolved in cc. alcohol; or

B. 5 g. of the beta-naphthoquinolinium-salt of 7-, 7-, dioxy- 2-, 2'- dinaphthylurea 5-, 5' disulfonic acid dissolved in 100 cc. alcohol; or

C. 5 g. of the cinchonin salt of the sulfuric acid ester of leucohexabromindigo.

On top of the first layer another colorless silver-bromide emulsion is coated which contains 2 g. diphenylquanidin acetate in a liter of emulsion. This emulsion may be sensitized to green light.

The film is thereafter exposed in a camera or in a printing machine, and subsequently developed and fixed in the usual manner.

After that the film is treated by immersing it into an aqueous solution containing either:

I. Diamine Pure Blue FF (Schultz l. c. No. 424); or

II. solution of the sodium salt of the sulfuric acid-ester of leucodibrombisthionaphthenindigo.

The dyestuil' in the deeper layer is formed diffusely if using a film according to Example A by diazotizing with a 1% solution of nitrous acid and subsequent coupling with a solution of naphthylaminchlorhydrate. Thus a red azo-dye-. stuffis formed.

Using a film as described in Example B by treating the film with a 0.5% solution of hydrobromic acid and sodium bichromate.

acid and sodium bichromate and thus a twocolor image is formed.

In the deeper layer a blue and in the upper layer a red image is formed locally.

It is already known to have a precipitating agent within a layer to be printed upon, but in this case only the small amounts of dyestufl of the matrix are transferred locally to the layer. In the present process the dyestuflf is uniformly applied from aqueous solutions and by the presence of precipitating agents determination of the amount of dyestufi and the selective dyeing of diiIerent strata of the material is rendered possible. 7

In the annexed drawing Figure 1 shows two differently sensitized silver halide layers I and II coated on to a support III.

Figure 2 shows two differently sensitized silver halide layers II and I on a support III. In each case layer I is uncolored and contains a precipitating agent for the dyestuif to be applied afterwards. Layer II is a colored layer. The layers containing the precipitating agent for the dyestufl' to be applied afterwards may contain a dyestuif which is not precipitated by the precipitating agent, but only acts as a filte dye during exposure and can be washed out after' react with the dyestuii to be used in coloring the said colloid, said precipitating agent being such as will not be adversely affected by ordinary photographic treating baths, exposing said material to light to form 'a silver image therein, treating the layer'througho'ut its depth after exposure, with an aqueous solution of said dyestufi to form a dyestufi precipitate only in said layer and treating said layer with a dyestuil' destroying bath which destroys the dyes-tuft locally in'proportion to the silver image in said layer.

2. The method of producing a colored photographic image in a gelatine layer of a photographic material, which comprises incorporating in a light sensitive silver halide gelatine emulsion used to form said layer, prior to exposure to light, a precipitating agent adapted to react with the dyestuii' to be used in coloring said layer, said precipitating agent being such as will not beadversely affected by ordinary photographic treating baths, exposing said layer to light to form a silver image therein; treating the layer throughout its depth after exposure, with an aqueous solution of said dyestufi to form a dye- 'an aqueous solution of said dyestufi to form a coloring saidlayer, said precipitating agent being 3. The method of producing a colored photographic image in a gelatine layer of aphotographic material, which comprises incorporating in a light sensitive silver halide emulsion, a precipitating agent adapted to react with the dye- 5 stufl to be used in coloring said layer, said precipitating agent being such as will not be adversely affected by ordinary photographic treating baths, pouring said silver halide gelatine emulsion having said precipitating agent incorporated therein to form a layer, exposing said layer to light to form a silver image therein, treating the layer throughout its depth after exposure, wlthan aqueous solution of said dyestufl to form a dyestufi precipitate only in said layer 5 and treating said layer-with adyestufl destroying bath which destroys the dyestufi locally in proportion to the silver image in said layer.

4. The method of producing a colored photographic image in a gelatine emulsion layer of a multi-layer. light sensitive silver halide material, which comprises incorporating in said layer prior to exposure of said material to light, a precipitating agent adapted to react with the dyestufl to be used in coloring said layer, said precipi- 5; tating agent being such as will not be adversely affected by ordinary'photographic treating baths, exposing said material to light to form a silver' image, treating said material after exposure with dyestuiI precipitate only in said layer and treating said material with a dyestufi destroying bath which destroys the dyestuil' locally in proportion to the silver image in said material. v 5. The method of producing a colored photographic image in a gelatine emulsion layer ofa multi-layer light sensitive photographic material, which comprises incorporating in a light sensitive silver halide emulsion a precipitating agent adapted to react with the dyestufi to be used in 40 such as will hot be adversely affected by ordinary photographic treating baths, pouring said silver halide gelatine'emulsion having said precipitating agent incorporated therein to form a layer along with the other layers of said material, exposing said material to light to form a silver image therein, treating said.material after exposure with an aqueous solution of said dyestuif to form a dyestuff precipitate only in said layer and treating said material with a dyestuif destraying bath which destroys the dyestufi locally in proportion to the silver image in said material. 6. The method of producing a colored photographic image in the layers of a multi-layer light sensitive silver halide material comprising a predyed layer and a layer to be-colored, which comprises incorporating'in the gelatine of the layer to be colored prior to exposure of said material to light, a precipitating agent adapted to react with the dyestufl to be used in coloring said layer, said precipitating agent being such as will notice adversely affected by ordinary photographic treating baths, exposing said material to light to form silver images therein, treating said material after exposure with an 2 aqueous solution of said dyestuii to form a dyeand treating said material with a dyestufi de; stroying bath which destroys the dyestuff locally in said layers in proportion to the silver images in said material.

. 7. The method of producing a colored photographic image in the layers of a multi-layer light sensitive silver halide material comprising a predyed layer and a layer to be colored, which, comprises incorporating in the gelatine of the layer to be colored prior to exposure oi said material to light, a basic precipitating agent adapted to react with an acid dyestuif to be used in coloring said layer, said precipitating agent being such as will not be adversely ailected by ordinary photographic treating baths, exposing said material to light to form silver images therein, treating said material after exposure with an aqueous solution of said dyestufl to form a dyestuii precipitate only in said layer to be colored and treating said material with a dyestufi destroying bath which destroys the dyestufi locally in said layers inproportion to the silver images in said materiaL.

8. The method of producing a colored photographic image in the layers of a multi-layer light sensitive silver halide material comprising a predyed layer and a layer to be colored, which comprises incorporating in the gelatine of the layer to be colored prior to exposure of said material to light, a precipitating agent comprising a salt of an organic base adapted to react with an acid dyestuii to be used in coloring said layer, said precipitating agent being such as will not be adversely aflected by ordinary photographic treating baths, exposing said material to light to form silver images therein, treating said material after exposure with an aqueous solution of said dyestuflf to form a dyestufl precipitate only in said layer to be colored and treating said material with a dyestufl destroying bath which destroys the dyestufl locally in said layers in proportion to the silver images in said material.

9. The method of producinga colored photographic image in the layers of a multi-layer light sensitive silver halide material comprising a predyed layer and a layer to be colored, which comprises incorporating in the gelatine of the layer' to be colored prior to exposure of said material to light, a precipitating agent comprising an acid adapted to react with a basic dyestuii' to be used in coloring said layer, said precipitating agent being such as will not be adversely airected by ordinary photographic treating baths, exposing said material to light to form silver images therein, treating said material after exposure with an aqueous solution of said dyestuif to form a dyestuff precipitate only in said layer to be colored and treating. said material with a dyestufi destroying bath which destroys the dyestufl locally in said layers in proportion to the silver photographic treating baths coated on top of a gelatine layer to be colored, which comprises incorporating in the gelatine of the layer to be colored prior to exposure of said material to light, a precipitating agent adapted to react with the dyestufl to be used in coloring said layer, said precipitating agent being such as will not be adversely affected by ordinary photographic treating baths, exposing the multi-layer material to light to form silver images therein, developing and fixing said silver images, treating said material after exposure with an aqueous solution of said dyestuiito form a dyestufi precipitate only in said layer to be colored, washing out the excess of said dyestuif from said material and treating said material with a dyestuii' destroying bath which destroys the dyestufl locally in said layers in proportion to the silver images in said material.

11. The method of producing multi-color photographic images which comprises incorporating in at least one layer of a multi-layer light sensi-' tive silver halide material, prior to exposure of said material to light, a precipitating agent adapted to react with the dyestuii to be used in coloring said layer, said precipitating agent being such as will not be adversely affected by ordinary photographic treating baths, exposing said material to light to form metallic silver images therein, applying an aqueous solution of said dyestuif to said material to produce a uniformly dyed silver image in said layer and treating said material with a dyestuff destroying bath which locally destroys the dyestufi in said layer in proportion to the metallic silver image therein.

12. A multi-layer photographic material comprising a predyed silver halide layer sensitized to a predetermined spectral range and asubstantially colorless silver halide layer sensitized to a difierent spectral range, said substantially colorless layer having incorporated therein a dyestuif precipitating agent selected from the group consisting of organic bases and salts of such bases which will not be adversely aflected by ordinary photographic treating baths.

13. A multi-layer photographic material comprising a substantially colorless silver halide layer containing a dye-forming substance and sensitized to a predetermined spectral range, and a substantially colorless silver halide layer sensitized to a difierent spectral range, said substantially colorless layer having incorporated therein a dyestufl precipitating agent selected from the group consisting of organic bases and salts of such bases which will not be adversely affected by ordinary photographic treating baths.

BELA GASPAR. 

